Asymmetric aryl phosphites

ABSTRACT

Compounds of the formula I ##STR1## in which x is 1, 2 or 3, and, if x=1, R 1  is C 1  -C 30  alkyl, C 1  -C 18  alkyl substituted by halogen, --COOR 2 , --CN, --NR 3  R 4  or by --CONR 3  R 4 , C 2  -C 18  alkyl which is interrupted by --NR 5  --, --O-- or --S--, C 3  -C 18  alkenyl, C 5  -C 12  cycloalkyl, phenyl-C 1  -C 4  alkyl, phenyl which is unsubstituted or substituted by C 1  -C 12  alkyl, halogen, phenyl-C 1  -C 4  alkyl and/or C 1  -C 4  alkoxy, or R 1  is naphthyl, a radical of the formula ##STR2##  R 2 , R 3 , R 4  and R 5 , independently of one another, are hydrogen, C 1  -C 18  alkyl, C 5  -C 12  cycloalkyl or phenyl-C 1  -C 4  alkyl, R 6  is hydrogen, methyl, allyl or benzyl, R 7  is hydrogen or --OR 9 , R 8  is hydrogen or methyl, R 9  is hydrogen or C 1  -C 30  alkyl, R 10  and R 11 , independently of one another, are hydrogen or C 1  -C 8  alkyl, and n is 3-6, with the proviso that R 1  is not a phenyl radical which is substituted in both ortho-positions to the carbon atom bonded to the oxygen atom, if x=2, R 1  is C 2  -C 18  alkylene, C 2  -C 18  alkylene which is interrupted by --NR 5  --, --O-- or --S--, or is a ##STR3##  radical, and, if x=3, R 1  is C 4  -C 12  alkanetriyl or a ##STR4##  group in which m is 1-4, are suitable as stabilisers for organic materials which are sensitive to thermal, oxidative and/or photoinduced degradation.

This application is a continuation of application Ser. No. 07/857,523,filed Mar. 25, 1992, abandoned.

The invention relates to novel phosphites, to the use thereof asstabilisers, to a novel phosphorochloridite as intermediate, and tocompositions containing said phosphites.

A number of patent applications, e.g. JP-A-54/039 455, JP-A-54/036 363,JP-A-54/055 043 and JP-A-62/086 036, disclose principally symmetricallysubstituted triaryl phosphites as stabilisers, and JP-A-54/041 948 usesthese phosphites together with other stabilisers in synthetic resincompositions. One of the concrete examples given here istris(2,4-di-tert-butyl-6-methylphenyl) phosphite. Phosphites containingat least one aryl radical are disclosed in JP-A-55/005 927, JP-A-54/163938, U.S. Pat. No. 4,348,308 and U.S. Pat. No. 3,558,554. The arylradical in U.S. Pat. No. 3,558,554 is preferably tert-butyl-substitutedp-cresyl. U.S. Pat. No. 4,348,308 discloses, for example, compounds suchas bis(2,4-di-tert-butylphenyl) cyclohexyl phosphite andbis(2-tert-butylphenyl) isodecyl phosphite. U.S. Pat. No. 4,444,929 usescompounds such as bis(2-tert-butyl-4-methylphenyl)2,6-di-tert-butyl-4-methylphenyl phosphite in stabiliser mixtures.Analogues of the intermediate for the preparation of the compoundsaccording to the invention have already been disclosed in theliterature. Thus, U.S. Pat. No. 4,584,146 and U.S. Pat. No. 4,444,929disclose bis(2,6-di-tert-butyl-4-methylphenyl) phosphorochloridite as anintermediate in the preparation of phosphites. U.S. Pat. No. 4,233,208uses bis(2,6-di-tert-butyl-4-methylphenyl) phosphorochloridite andsimilar chlorides and hydroxides as stabilisers.

There continues to be a demand for effective stabilisers for organicmaterials which are sensitive to photoinduced and/or thermooxidativedegradation.

The invention relates to compounds of the formula I ##STR5## in which xis 1, 2 or 3, and, if x=1, R¹ is C₁ -C₃₀ alkyl, C₁ -C₁₈ alkylsubstituted by halogen, --COOR², --CN, --NR³ R⁴ or by --CONR³ R⁴, C₂-C₁₈ alkyl which is interrupted by --NR⁵ --, --O-- or --S--, C₃ -C₁₈alkenyl, C₅ -C₁₂ cycloalkyl, phenyl-C₁ -C₄ alkyl, phenyl which isunsubstituted or substituted by C₁ -C₁₂ alkyl, halogen, phenyl-C₁ -C₄alkyl and/or C₁ -C₄ alkoxy, or R₁ is naphthyl, a radical of the formula##STR6## R₂, R₃, R₄ and R₅, independently of one another, are hydrogen,C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl or phenyl-C₁ -C₄ alkyl, R⁶ ishydrogen, methyl, allyl or benzyl, R⁷ is hydrogen or --OR⁹, R⁸ ishydrogen or methyl, R⁹ is hydrogen or C₁ -C₃₀ alkyl, R¹⁰ and R¹¹,independently of one another, are hydrogen or C₁ -C₈ alkyl, and n is3-6, with the proviso that R¹ is not a phenyl radical which issubstituted in both ortho-positions to the carbon atom bonded to theoxygen atom,

if x=2, R¹ is C₂ -C₁₈ alkylene, C₂ -C₁₈ alkylene which is interrupted by--NR⁵ --, --O-- or --S--, or is a ##STR7## radical, and, if x=3, R¹ isC₄ -C₁₂ alkanetriyl or a ##STR8## group in which m is 1-4.

C₁ -C₃₀ alkyl R¹ may be linear or branched and is, for example, methyl,ethyl, isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, icosyl, tetracosyl ortriacontyl. Alkyl R¹ is in particular C₁ -C₂₄ alkyl, very particularlyC₁ -C₁₈ alkyl, preferably C₁ -C₁₂ alkyl, e.g. C₁ -C₄ alkyl.

C₁ -C₁₈ alkyl R², R³, R⁴ and R⁵ may be linear or branched and aredefined, for example, as for C₁ -C₃₀ alkyl R¹ apart from thecorresponding number of carbon atoms. Preference is given to C₁ -C₁₂alkyl, in particular C₁ -C₄ alkyl.

Halogen-substituted C₁ -C₁₈ alkyl R¹ may be linear or branched andmonosubstituted or polysubstituted, e.g. monosubstituted totrisubstituted, in particular monosubstituted or disubstituted, and is,for example, chloromethyl, dichloromethyl, trichloromethyl, chloroethyl,dichloroethyl, chloropropyl, fluoromethyl, trifluoromethyl,trifluoroethyl, trifluoropropyl, etc.

--COOR² -substituted C₁ -C₁₈ alkyl R¹ is, for example, methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl oroctadecyl, each of which is substituted by methoxycarbonyl,ethoxycarbonyl, isomers of propoxycarbonyl, butoxycarbonyl,pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl,ethylhexyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl,cyclohexyloxycarbonyl, or tolyloxycarbonyl, in particular bymethoxycarbonyl or ethoxycarbonyl, and is preferably methyl or ethyl, inparticular methyl, each of which is substituted by methoxycarbonyl,ethoxycarbonyl or in particular butoxycarbonyl.

--CONR³ R⁴ -substituted C₁ -C₁₈ alkyl R¹ is, for example, methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl oroctadecyl, each of which is substituted by dimethylaminocarbonyl,diethylaminocarbonyl, dibutylaminocarbonyl or ethylmethylaminocarbonyl,in particular dimethyl- or diethylaminocarbonyl, and is preferablymethyl, ethyl or propyl, each of which is substituted bydimethylaminocarbonyl or diethylaminocarbonyl, in particular propylwhich is substituted by dimethylaminocarbonyl.

CN-substituted C₁ -C₁₈ alkyl R¹ is, for example, cyanomethyl,cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl,cyanooctyl, cyanodecyl, cyanododecyl or cyanooctadecyl, in particularcyanoethyl.

C₂ -C₁₈ Alkyl R¹ which is interrupted by --O--, --S-- or --NR⁵ -- unitscontain, for example, the structural units --CH₂ --CH₂ --O--, --CH₂--CH₂ --S-- or --CH₂ --CH₂ --NR⁵ --. The --NR⁵ --, --O-- or --S-- groupscan occur once or more than once in the chain. Other examples of C₂ -C₁₈alkyl R¹ which is interrupted by --O--, --S-- or --NR⁵ -- units aremethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, dodecyl or octadecyl, each of which is substituted by methoxy,ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio,dimethylamino, diethylamino, dipropylamino, etc, in particular methoxyor ethoxy, preferably ethyl which is substituted by methoxy.

C₅ -C₁₂ Cycloalkyl R¹, R², R³, R⁴ and R⁵ may be, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl orcyclododecyl, preferably cyclopentyl or cyclohexyl, in particularcyclohexyl.

Phenyl-C₁ -C₄ alkyl R¹, R², R³, R⁴ and R⁵ are, for example, benzyl,1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α-methylbenzyl,α,α-dimethylbenzyl, etc, preferably benzyl or 1-phenylethyl.

An aromatic radical R¹ is preferably phenyl.

Substituted phenyl R¹ preferably contains 1 to 3 substituents, inparticular 1 or 2 substituents, and is, for example, chlorophenyl,dichlorophenyl, trichlorophenyl, fluorophenyl, difluorophenyl, tolyl,dimethylphenyl, mesityl, ethylphenyl, diethylphenyl, isopropylphenyl,tert-butylphenyl, benzylphenyl, phenylethylphenyl, di-t-butylphenyl,methyl-di-tert-butylphenyl, dodecylphenyl, methoxyphenyl,dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methoxyethylphenyl orethoxymethylphenyl, in particular p-tert-butylphenyl. Alkyl and alkoxyas aryl substituents preferably have 1-4 carbon atoms and are, inparticular, methyl, tert-butyl or methoxy, preferably tert-butyl.

An aromatic radical R¹ is in particular phenyl which is unsubstituted orsubstituted by an alkyl group.

Halogen is, in particular, chlorine, bromine or fluorine.

Of particular interest are compounds of the formula I in which, if x=1,R¹ is C₁ -C₃₀ alkyl, C₁ -C₁₈ alkyl substituted by halogen, --COOR²,--CN, --NR³ R⁴ or by --CONR³ R⁴, C₂ -C₁₈ alkyl which is interrupted by--NR⁵ --, --O-- or --S--, C₃ -C₁₈ alkenyl, C₅ -C₁₂ cycloalkyl, phenyl-C₁-C₄ alkyl, phenyl which is unsubstituted or substituted by C₁ -C₁₂alkyl, halogen, phenyl-C₁ -C₄ alkyl and/or C₁ -C₄ alkoxy, or R₁ isnaphthyl, a radical of the formula ##STR9## if x=2, R¹ is C₂ -C₁₈alkylene, C₂ -C₁₈ alkylene which is interrupted by --NR⁵ --, --O-- or--S--, or is a ##STR10## radical, and, if x=3, R¹ is C₄ -C₁₂ alkanetriylor a ##STR11## group in which m is 1-4.

Other particularly interesting compounds of the formula I are those inwhich, if x=1, R¹ is C₁ -C₂₄ alkyl, C₁ -C₁₂ alkyl substituted byhalogen, --COOR², --CN, --NR³ R⁴ or by --CONR³ R⁴, C₂ -C₁₈ alkyl whichis interrupted by --NR⁵ --, --O-- or --S--, C₃ -C₁₈ alkenyl, C₅ -C₁₂cycloalkyl, phenyl-C₁ -C₄ alkyl, phenyl which is unsubstituted orsubstituted by C₁ -C₁₂ alkyl, halogen, phenyl-C₁ -C₄ alkyl and/or C₁ -C₄alkoxy, or R₁ is naphthyl, a radical of the formula ##STR12## if x=2, R¹is C₂ -C₁₂ alkylene, C₂ -C₁₂ alkylene which is interrupted by --NR⁵ --,--O-- or --S--, or is a ##STR13## radical, and R¹⁰ and R¹¹,independently of one another, are hydrogen or C₁ -C₄ alkyl, and,

if x=3, R¹ is C₄ -C₁₂ alkanetriyl or a ##STR14## group in which m is1-4.

Preference is given to compounds of the formula I in which, if x=1, R¹is C₁ -C₂₀ alkyl, C₁ -C₈ alkyl which is substituted by halogen, --COOR²,--CN or --NR³ R⁴, C₂ -C₈ alkyl which is interrupted by --O-- or --S--,C₃ -C₈ alkenyl, C₅ -C₈ cycloalkyl, phenyl which is unsubstituted orsubstituted by C₁ -C₁₂ alkyl or phenyl-C₁ -C₄ alkyl, or R₁ is naphthyl,a radical of the formula ##STR15## R⁶ is hydrogen or methyl, and R⁸ andR⁹ are hydrogen, if x=2, R¹ is C₂ -C₈ alkylene or C₂ -C₈ alkylene whichis interrupted by --NR⁵ -- or --O--, and,

if x=3, R¹ is a ##STR16## radical.

Further interesting compounds of the formula I are those in which, ifx=1, R¹ is C₁ -C₁₈ alkyl which is unsubstituted or substituted byhalogen, --COOR², --CN or --NR³ R⁴, C₂ -C₁₈ alkyl which is interruptedby --NR⁵ --, --O-- or --S--, C₃ -C₆ alkenyl, C₅ -C₈ cycloalkyl,phenyl-C₁ -C₄ alkyl, a radical of the formula ##STR17## and, if x=2, R¹is C₂ -C₁₂ alkylene, C₂ -C₁₂ alkylene which is interrupted by --NR⁵ --,--O-- or --S--, or is a ##STR18## radical, and, if x=3, R¹ is C₄ -C₁₂alkanetriyl or a ##STR19## group.

Preference is given to compounds of the formula I in which x=1, R¹ is C₁-C₁₂ alkyl which is unsubstituted or substituted by halogen, --COOR²,--CN or --NR³ R⁴, C₂ -C₁₂ alkyl which is interrupted by --NR⁵ --, --O--or --S--, or is phenyl-C₁ -C₄ alkyl or C₅ -C₇ cycloalkyl.

Preference is furthermore given to compounds of the formula I in whichR¹ is C₁ -C₄ alkyl.

Particular emphasis should also be attached to compounds of the formulaI in which R¹ is as defined above, but is not unsubstituted or C₁ -C₁₂alkyl-, halogen- or C₁ -C₄ alkoxy-substituted phenyl or naphthyl.

Also worthy of mention in particular are compounds of the formula I inwhich R¹ is C₁ -C₁₈ alkyl, C₅ -C₇ cycloalkyl or phenyl-C₁ -C₄ alkyl, inparticular C₁ -C₁₈ alkyl.

The compounds of the formula I can be obtained by processes which areknown per se in chemistry. DE-A-2 950 694 describes a process for thepreparation of corresponding compounds by reacting a phosphorustrihalide, a phosphorous acid monoester dihalide or a phosphorous aciddiester halide with a phenol in the presence of an alkali metalhydroxide or alkaline earth metal hydroxide.

The compounds according to the invention can accordingly be prepared bysubstituting the chlorine in the diaryl phosphorochloridite by analcohol or a phenol in the presence of a base. ##STR20##

R¹ is as defined above.

In order to prepare dimeric and trimeric compounds of the formula I, thecorresponding polyols are used.

The bases used can be organic bases or inorganic bases. Examples oforganic bases are tertiary amines, e.g. trimethylamine, triethylamine,N,N-dimethylaniline, N,N-diethylaniline or pyridine. Examples ofinorganic bases are alkali metal hydroxides, for example sodiumhydroxide or potassium hydroxide, or alkali metal carbonates, forexample sodium carbonate or potassium carbonate.

The substitution reaction temperatures are, for example, from -30° C. to+150° C., preferably from -10° C. to +70° C.

Solvents which can be employed are aliphatic and aromatic, simple orhalogenated hydrocarbons or ethers. Examples of suitable aromatichydrocarbons are benzene, toluene and xylene, and an example of asuitable chlorinated aromatic hydrocarbon is chlorobenzene. Examples ofaliphatic hydrocarbons which can be used as solvents are hexane, pentaneand further petroleum ether fractions. Examples of suitable halogenatedaliphatic hydrocarbons are methylene chloride and chloroform. Examplesof suitable ethers are diethyl ether, dibutyl ether and tetrahydrofuran.

The diaryl phosphorochloridite (II) and the alcohol R¹ OH areexpediently employed in equivalent amounts. It is, however, alsopossible, for example, to use an excess of alcohol, for example 1.05-1.2equivalents.

A further method of preparing compounds according to the invention is tocondense 2 equivalents of 2,4-di-tert-butyl-6-methylphenol with oneequivalent of a phosphorus compound R¹ O-PCl₂ in the presence of anorganic base.

The invention also relates to the compound of the formula II ##STR21##and to the use thereof for the preparation of compounds of the formulaI.

The preparation of phosphorochloridites is known to persons skilled inthe art and is described in numerous publications. The novelphosphorochloridite of the formula II can be prepared by analogousprocesses. For instance, H. G. Cook et al., J. Chem. Soc. 1949, IV,2921-2927, and A. J. Razumov et al., Chemical Abstracts 60, 1571 g(1964), describe the preparation of corresponding chlorides by reactingphosphorus trichloride with alkanols in the presence ofN,N-dimethylaniline or N,N-diethylaniline as acid acceptor. J. Michalskiet al., J. Chem. Soc. 1961, 4904, disclose a variant of this process inwhich the acid acceptor employed is a pyridine/diethylaniline mixture.Reactions of phosphorus trichloride with hindered phenols are disclosedin U.S. Pat. No. 3,281,506 and U.S. Pat. No. 4,584,146. H. G. Cook etal., J. Chem. Soc., 1949, IV, 2921-2927 indicate a further method ofpreparing phosphorochloridites analogous to the formula II. They reactphosphorus trichloride with symmetrical trialkyl phosphites. A variantof this process is described in U.S. Pat. No. 4,079,103.

Bis(2,4-di-tert-butyl-6-methyl) phosphorochloridite can also be prepareddirectly in the melt without solvents. This allows the preparation ofthe phosphites of the formula I without isolation of the intermediate.

The compounds of the formula I are highly suitable for stabilisingorganic materials against photoinduced, thermal and/or oxidativedegradation. The invention therefore also relates to compositionscomprising an organic material which is sensitive to degradationreactions of this type, and at least one compound of the formula I, andto the use of compounds of the formula I as stabilisers for organicmaterials against said types of degradation.

Examples of such materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, polymethylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE) and linear low density polyethylene (LLDPE).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene-propylene copolymers, linear lowdensity polyethylene (LLDPE) and its mixtures with low densitypolyethylene (LDPE), propylene-but-1-ene, propylene-isobutylene,ethylene-but-1-ene, ethylene-hexene, ethylene-methylpentene,ethylene-heptene, ethylene-octene, propylene-butadiene,isobutylene-isoprene, ethylene-alkyl acrylate, ethylene-alkylmethacrylate, ethylene-vinyl acetate or ethylene-acrylic acid copolymersand their salts (ionomers) and terpolymers of ethylene with propyleneand a diene, such as hexadiene, dicyclopentadiene orethylidenenorbornene; as well as mixtures of such copolymers and theirmixtures with polymers mentioned in 1), for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers, LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinylacetate copolymers and LLDPE/ethylene-acrylic acid copolymers.

3a. Hydrocarbon resins (for example C₅ -C₉) and hydrogenatedmodifications thereof (for example tackifiers).

4. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

5. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene-butadiene, styrene-acrylonitrile,styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate,styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; highimpact strength mixtures of styrene copolymers and another polymer, forexample a polyacrylate, a diene polymer or an ethylene-propylene-dieneterpolymer; and block copolymers of styrene, for examplestyrene-butadiene-styrene, styrene-isoprene-styrene,styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

6. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene-propylene-diene terpolymers, styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate-butadiene copolymers, as well as mixturesthereof with the copolymers mentioned under 5), for instance thecopolymer mixtures known as ABS, MBS, ASA or AES polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubber, chlorinated or chlorosulfonated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,in particular polymers from halogen-containing vinyl compounds, forexample polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof, for examplevinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate orvinylidene chloride-vinyl acetate copolymers.

8. Polymers derived from α,β-unsaturated acids and derivatives thereof,such as polyacrylates and polymethacrylates, polyacrylamides andpolyacrylonitriles.

9. Copolymers from the monomers mentioned under 8) with each other orwith other unsaturated monomers, for instance acrylonitrile-butadiene,acrylonitrile-alkyl acrylate, acrylonitrile-alkoxyalkyl acrylate oracrylonitrile-vinyl halide copolymers or acrylonitrile-alkylmethacrylate-butadiene terpolymers.

10. Polymers derived from unsaturated alcohols and amines, or acylderivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallylmelamine;and their copolymers with olefins mentioned in 1) above.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain comonomers, for example ethylene oxide; polyacetalsmodified with thermoplastic polyurethanes, acrylates or MBS.

13. Polyphenylene oxides and sulfides, and mixtures thereof with styrenepolymers or polyamides.

14. Polyurethanes derived from polyethers, polyesters or polybutadieneswith terminal hydroxyl groups on the one hand and aliphatic or aromaticpolyisocyanates on the other, and precursors thereof.

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as nylon 4, nylon 6, nylon 6/6, 6/10, 6/9,6/12 and 4/6, nylon 11, nylon 12, aromatic polyamides obtained fromm-xylene, diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic and/or terephthalic acid andoptionally an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide. Block copolymers of the aforementioned polyamides withpolyolefins, olefin copolymers, ionomers or chemically bonded or graftedelastomers; or with polyethers, for instance with polyethylene glycol,polypropylene glycol or polytetramethylene glycol. Further, EPDM-orABS-modified polyamides or copolyamides; and polyamides condensed duringprocessing ("RIM polyamide systems").

16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

17. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates aswell as block polyether-esters derived from polyethers having hydroxylend groups; also polycarbonate- or MBS-modified polyesters.

18. Polycarbonates and polyester carbonates.

19. Polysulfones, polyether sulfones and polyether ketones.

20. Crosslinked polymers derived from aldehydes on the one hand andphenols, urea or melamine on the other, such as phenol/formaldehyderesins, urea/formaldehyde resins and melamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols, and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low inflammability.

23. Crosslinkable acrylic resins, derived from substituted acrylicesters, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

25. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, natural rubber, gelatin andderivatives thereof which are chemically modified in apolymer-homologous manner, such as cellulose acetates, cellulosepropionates and cellulose butyrates, or cellulose ethers, such asmethylcellulose; and colophony resins and their derivatives.

27. Mixtures (polyblends) of polymers as mentioned above, for examplePP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

28. Naturally occuring and synthetic organic substances which are puremonomeric compounds or mixtures thereof, for example mineral oils,animal or vegetable fats, oils and waxes, or oils, waxes and fats basedon synthetic esters (for example phthalates, adipates, phosphates ortrimellitates), and blends of synthetic esters with mineral oils in anydesired weight ratios, as used, for example, as spinning preparations,and aqueous emulsions thereof.

29. Aqueous emulsions of natural or synthetic rubbers, for examplenatural rubber latex or latexes of carboxylated styrene-butadienecopolymers.

The organic materials to be protected are preferably natural,semisynthetic or preferably synthetic organic materials. Particularpreference is given to thermoplastic polymers, in particular PVC orpolyolefins, for example polyethylene and polypropylene (PP).

The compositions according to the invention expediently contain thecompounds of the formula I in amounts of from 0.01 to 10% by weight, forexample from 0.05 to 5% by weight, preferably from 0.05 to 3% by weight,but in particular from 0.1 to 2% by weight. It is possible for thecompositions to contain one or more compounds of the formula I, and thepercent by weight data relate to the total amount of these compounds.The calculation is based on the total weight of the organic materialwithout the compounds of the formula I. Incorporation into the materialscan be effected, for example, by mixing in or applying the compounds ofthe formula I and, if desired, further additives by methods which areconventional in industry. If the materials are polymers, in particularsynthetic polymers, incorporation can take place before or duringmoulding or by applying the dissolved or dispersed compounds to thepolymer, if necessary with subsequent evaporation of the solvent. In thecase of elastomers, these may also be stabilised as latexes. A furtherway of incorporating the compounds of the formula I into polymers is toadd them before, during or immediately after the polymerisation of thecorresponding monomers or before the crosslinking. The compounds of theformula I can be added as such or in encapsulated form (for example inwaxes, oils or polymers). If added before or during the polymerisation,the compounds of the formula I can also act as regulators for the chainlength of the polymers (chain terminators).

The compounds of the formula I or mixtures thereof can also be added tothe plastics to be stabilised in the form of a masterbatch whichcontains these compounds, for example, in a concentration of from 2.5 to25% by weight.

Incorporation of the compounds of the formula I can expediently beeffected by the following methods:

as an emulsion or dispersion (for example to latexes or emulsionpolymers)

as a dry mix during mixing of the additional components or polymermixtures

by direct addition into the processing apparatus (for example extruder,internal mixer, etc)

as a solution or melt.

Polymer compositions according to the invention can be used in varousforms or converted into various products, for example as (into) films,fibres, tapes, moulding compositions, profiles or as binders for surfacecoatings, adhesives or adhesive cements.

As stated above, the organic materials to be protected are organic,preferably synthetic polymers. Particular preference is given to theprotection of thermoplastic materials, in particular polyolefins. Theexcellent effectiveness of the compounds of the formula I as processingstabilisers (heat stabilisers) should be particularly emphasised. Forthis purpose, they are advantageously added to the polymer before orduring processing thereof.

However, it is also possible to stabilise other polymers (for exampleelastomers) or lubricants or hydraulic fluids against degradation, forexample photoinduced and/or thermooxidative degradation. Elastomers aregiven in the above list of possible organic materials.

Suitable lubricants and hydraulic fluids are based, for example, onmineral or synthetic oils or mixtures thereof. The lubricants are knownto persons skilled in the art and are described in the relevantspecialist literature, for example in Dieter Klamann, "Schmierstoffe undverwandte Produckte" ]Lubricants and Related Products] (Verlag Chemie,Weinheim, 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" [TheLubricant Handbook] (Dr. Alfred Huthig-Verlag, Heidelberg, 1974), and in"Ullmanns Enzyklopadie der technischen Chemie" [Ullmann's Encyclopaediaof Industrial Chemistry], Vol. 13, pages 85-94 (Verlag Chemie, Weinheim,1977).

The invention also relates to the stabilisation of organic materialsagainst oxidative, thermal and/or actinic degradation by adding orapplying, as stabilisers, compounds of the formula I to this material.

In addition to the compounds according to the invention, thecompositions according to the invention, in particular if they containorganic, preferably synthetic polymers, may also contain furtherconventional additives. Examples of such additives are:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-di-nonyl-4-methylphenol.

1.2. Alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone and 2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol) and4,4'-thiobis(6-tert-butyl-2-methylphenol).

1.4. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol),2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2'-methylenebis(4-methyl-6-cyclohexylphenol),2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2'methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4'-methylenebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene andbis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the calciumsalt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.6. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide,2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazineand octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmonohydric or polyhydric alcohols, for example with methanol,octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith monohydric or polyhydric alcohols, for example with methanol,octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxy)ethyl isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.

1.9. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmonohydric or polyhydric alcohols, for example with methanol,octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxy)ethyl isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.

1.10. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, forexampleN,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamineand N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

2. UV absorbers and light stabilisers

2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl,3',5'-di-tert-butyl, 5'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl),5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl,3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and3',5'-bis(α,α-dimethylbenzyl) derivatives.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy, 4-decycloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted or unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl isooctyl α-cyano-β,β-diphenylacrylate,methyl α-carbomethoxycinnamate, methyl or butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5 Nickel compounds, for example nickel complexes of2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1complex or the 1:2 complex, if appropriate with additional ligands, suchas n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl4-hydroxy-3,5-di-tert-butylbenzylphosphonates, such as the methyl orethyl ester, nickel complexes of ketoximes, such as2-hydroxy-4-methylphenyl undecyl ketoxime, and nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethylpiperidyl) sebacate,bis(1,2,2,6,6-pentamethylpiperidyl) sebacate,bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensationproduct formed from1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperdine and succinic acid,the condensation product formed fromN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetraoate and1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone).

2.7. Oxalic acid diamides, for example 4,4'-di-octyloxyoxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyloxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyloxanilide,2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and a mixture thereof with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide or mixtures of o-methoxy-and p-methoxy-disubstituted oxanilides and of o-ethoxy- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2, 4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazineand2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxalamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole and bis(benzylidene)oxalodihydrazide.

4. Further phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythirtyl diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythrityl diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite, tristearyl sorbitol triphosphite,tetrakis-(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphonite and3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

5. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl and tridecyl esters,mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide and pentaerythrityltetrakis (β-dodecylmercapto)propionate.

6. Benzofuranones and indolinones, as described, for example, in WO-A80/01 566 and EP-A 415 887.

7. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

8. Basic costabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali and alkalineearth metal salts of higher fatty acids, for example calcium stearate,zinc stearate, magnesium stearate, sodium ricinoleate and potassiumpalmitate, antimony pyrocatecholate and tin pyrocatecholate.

9. Nucleating agents, for example 4-tert-butylbenzoic acid, adipic acidand diphenylacetic acid.

10. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black and graphite.

11. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, antistatic andblowing agents.

The examples below illustrate the invention in greater detail. Parts andpercentages, as in the claims and the remainder of the description, areby weight, unless stated otherwise.

EXAMPLE 1 Preparation of bis(2,4-di-tert-butyl-6-methylphenyl)phosphorochloridite

890.3 g (4 mol) of 2,4-di-tert-butyl-6-methylphenol, 4.2 g ofdimethylformamide and 170.0 g of xylene are introduced into a four-neckflask which has been flushed with nitrogen and is fitted with athermometer, dropping funnel, reflux condenser and distillationattachment. 274.9 g (2 mol) of phosphorus trichloride are added dropwisewith stirring over the course of 1.5 hours at a temperature of 50° C.The reaction mixture is warmed to 130° C. and refluxed at thistemperature for 1 hour. The reaction mixture is kept at 120° C. for 1hour under a vacuum of 0.15 bar. Xylene is subsequently removed bydistillation under a greater vacuum. After the vacuum has been brokenusing nitrogen, 959.5 g (1.9 mol) of the title compound are obtained assupercooled, yellow-orange, clear melt.

Purity: 98% (determined using ³¹ P-NMR)

Purification: distillation at 204° C./0.0002 bar.

EXAMPLE 2 Preparation of bis(2,4-di-tert-butyl-6-methylphenyl) methylphosphite

300 g (1.36 mol) of 2,4-di-tert-butyl-6-methylphenol are introduced intoa 1500 ml sulfonation flask fitted with thermometer, stirrer and refluxcondenser, and the reactor is flushed with nitrogen. The mixture iswarmed to 55° C. in order to melt the phenol, and 1.5 g ofdimethylformamide are added to the melt. 102.7 g (0.75 mol) ofphosphorus trichloride are added dropwise over the course of 1.5 hoursat the same temperature. The hydrochloric acid gas produced isneutralised by means of a 30% aqueous sodium hydroxide solution. Whenthe addition is complete, the reaction mixture is heated to 140° C. overthe course of 4 hours and stirred at this temperature for a furtherhour. A slight vacuum (0.55 bar) is then applied, and the mixture isstirred at 130° C. for a further 4 hours. The clear yellow-orange meltobtained (=bis(2,4-di-tert-butyl-6-methyl) phosphorochloridite) is thenallowed to cool to about 80° C. in a nitrogen atmosphere and is dilutedwith 500 ml of petroleum ether (80°-100° C.). The solution is cooled to-5° C., and 89.3 g (0.884 mol) of triethylamine are added over thecourse of 15 minutes. 32.8 g (1.02 mol) of methanol are then addeddropwise over the course of 1 hour, during which the temperature risesto +5° C. and the triethylamine hydrochloride precipitates. This mixtureis allowed to warm slowly (about 1 hour) to room temperature withstirring. The precipitate is filtered off and the filtrate isevaporated, giving 328 g of phosphite as a yellow oil (purity determinedby high pressure liquid chromatography [HPLC]: 94%). Recrystallisationof the crude product from ethanol gives 262 g (77% of theory) of thetitle compound in the form of a white powder having a melting point of75°-78° C.

Elemental analysis: P calc.: 6.19% found: 6.19%

EXAMPLES 3-33

The compounds of Examples 3-33 are prepared analogously to the compoundof Example 2 using the alcohol or phenol corresponding to thesubstituent R¹. The substituents and analytical data are shown in Table1 below. ##STR22##

                                      TABLE 1                                     __________________________________________________________________________    Example              Yield                                                                             Melting point [°C.]                                                               Elemental analysis                        No.  R.sub.1         [%] Refractive index n.sub.D.sup.20                                                          % P calc.                                                                           % P found                           __________________________________________________________________________    3    C.sub.2 H.sub.5 65  91         6.02  6.01                                4    n-C.sub.3 H.sub.7                                                                             60  57-58      5.86  5.70                                5    i-C.sub.3 H.sub.7                                                                             64  104-105    5.86  5.80                                6    n-C.sub.6 H.sub.13                                                                            99  high viscosity                                                                           5.43  5.49                                                     95  1.5173     5.17  5.16                                8    n-C.sub.12 H.sub.25                                                                           98  1.5107     4.73  4.71                                9    i-C.sub.10 H.sub.21                                                                           95  high viscosity                                                                           4.94  4.99                                10   i-C.sub.12/13 H.sub.25/27                                                                     79  high viscosity                                                                           4.67  4.65                                11   n-C.sub.18 H.sub.37                                                                           93  1.5061     4.19  4.19                                12   i-C.sub.18 H.sub.37                                                                           91  1.5036     4.19  4.10                                13   (CH.sub.2).sub.2 OCH.sub.3                                                                    70  yellowish oil                                                                            5.69  5.44                                14   (CH.sub.2 CH.sub.2 O) .sub.3C.sub.4 H.sub.9                                                   97  1.5119     4.59  4.48                                15   (CH.sub.2).sub.2 SC.sub.2 H.sub.5                                                             98  high viscosity                                                                           5.39  5.18                                16   (CH.sub.2).sub.2 CF.sub.3                                                                     72  72         5.45  5.40                                17   (CH.sub.2).sub.2 CN                                                                           55  139        5.74  5.70                                18   (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                            65  yellowish oil                                                                            5.42  5.30                                19   CH.sub.2 CO.sub.2.sup.n C.sub.4 H.sub.9                                                       96  high viscosity                                                                           5.16  4.90                                20   benzyl          97  high viscosity                                                                           5.37  5.46                                21   (CH.sub.2).sub.2 C.sub.6 H.sub.5                                                              74  78-80      5.24  5.18                                22   cyclohexyl      64  high viscosity                                                                           5.45  5.22                                23   phenyl          80  96-98      5.50  5.52                                24   naphthyl        83  101-103    5.05  4.97                                25                                                                                  ##STR23##      55  154-156    5.00  4.99                                26                                                                                  ##STR24##      97  high viscosity                                                                           4.50  4.53                                27                                                                                  ##STR25##      99  1.5508     4.55  4.30                                28                                                                                  ##STR26##      78  117-120    4.59  4.44                                29                                                                                  ##STR27##      54  63-70      4.84  4.79                                30                                                                                  ##STR28##      32  55-75      4.95  4.81                                31                                                                                  ##STR29##      87  69-78      4.62  4.60                                32   CH.sub.2 CHCH.sub.2                                                                           63  81-82      5.88  5.84                                33                                                                                  ##STR30##      25  high viscosity                                                                           4.39  4.23                                __________________________________________________________________________

EXAMPLES 34-36 ##STR31##

The compounds of Examples 34-36 are prepared analogously to the compoundof Example 2 using the polyol corresponding to the substituent R¹. Twoequivalents of both bis(2,4-di-tert-butyl-6-methyl) phosphorochloriditeand base are used for the compounds where x=2, and three equivalents ofbis(2,4-di-tert-butyl-6-methyl) phosphorochloridite and threeequivalents of base are correspondingly used for the trimeric compound(x=3). The substituents and analytical data are shown in Table 2 below.

                                      TABLE 2                                     __________________________________________________________________________    Example              Yield                                                                             Melting point [°C.]                                                               Elemental analysis                        No.  R.sub.1       x [%] Refractive index n.sub.D.sup.20                                                          % P calc.                                                                           % P found                           __________________________________________________________________________    34   (CH.sub.2).sub.6                                                                            2 49  168        5.87  5.82                                35   (CH.sub.2).sub.2 O(CH.sub.2).sub.2                                                          2 75  40-50 (amorphous)                                                                        5.94  5.36                                36                                                                                  ##STR32##    3 63  136-137    5.86  5.74                                __________________________________________________________________________

EXAMPLE 37 Stabilisation of polypropylene

1.3 kg of polypropylene powder (melt flow index 3.2 g/10 min, measuredat 230° C./2.16 kg) are mixed with 0.05% of calcium stearate, 0.05% oftetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and0.05% of the stabiliser indicated in Table 3. This mixture is extrudedat 100 rpm in an extruder having a barrel diameter of 20 mm and a lengthof 400 mm, the 3 heating zones being set at 260° C., 270° C. and 280° C.The extrudate is cooled by drawing through a waterbath and issubsequently granulated. The granules obtained are extruded a second andthird time. After these three extrusions, the melt flow index ismeasured at 230° C./2.16 kg. Small values indicate good stabilisation.The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Compound from   Melt flow index                                               Example No.     [g/10 min]                                                    ______________________________________                                        --              17.8                                                          2               6.1                                                           3               6.6                                                           4               5.8                                                           5               10.2                                                          6               6.0                                                           7               6.7                                                           8               5.8                                                           9               6.2                                                           10              8.7                                                           11              7.1                                                           12              7.0                                                           13              8.7                                                           16              9.5                                                           ______________________________________                                    

EXAMPLE 38 Stabilisation of polyethylene

100 parts of unstabilised high-density polyethylene having a molecularweight of about 500,000 in powder form are mixed in the dry state with0.05 part oftetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and0.1 part of the stabiliser indicated in Table 4. The mixture is kneadedfor 50 minutes at 220° C. and 50 rpm in a Brabender Plastograph. Duringthis time, the kneading resistance is recorded continuously as torque.As a consequence of the crosslinking of the polymer, a rapid increase intorque occurs during the kneading time after initially remainingconstant. The effectiveness of the stabilisers is apparent from anincrease in the time before the torque increases. The values obtainedare shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Compound from  Time before increase                                           Example No.    in torque [min]                                                ______________________________________                                        --             5.0                                                            2              16.5                                                           3              12.0                                                           4              12.0                                                           5              13.0                                                           6              15.0                                                           7              22.5                                                           8              17.0                                                           9              19.0                                                           10             16.5                                                           11             14.0                                                           12             17.0                                                           13             13.5                                                           16             15.0                                                           ______________________________________                                    

What is claimed is:
 1. A composition comprising(a) an organic materialwhich is sensitive to oxidative, thermal and/or photoinduceddegradation, and (b) an effective stabilizing amount of at least onecompound of formula I ##STR33## in which x is 1, 2 or 3, and, if x=1, R¹is C₁ -C₃₀ alkyl, C₁ -C₁₈ alkyl substituted by halogen, --COOR², --CN,--NR³ R⁴ or by --CONR³ R⁴, C₂ -C₁₈ alkyl which is interrupted by --NR⁵--, --O-- or --S--, C₃ -C₁₈ alkenyl, C₅ -C₁₂ cycloalkyl, phenyl-C₁ -C₄alkyl, unsubstituted phenyl, or R¹ is naphthyl, a radical of the formula##STR34## R², R³, R⁴ and R⁵, independently of one another, are hydrogen,C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl or phenyl-C₁ -C₄ alkyl, R⁶ ishydrogen, methyl, allyl or benzyl, R⁷ is hydrogen or --OR⁹, R⁸ ishydrogen or methyl, R⁹ is hydrogen or C₁ -C₃₀ alkyl, R¹⁰ and R¹¹,independently of one another, are hydrogen or C₁ -C₈ alkyl, and n is3-6, with the proviso that R¹ is not a phenyl radical which issubstituted in both ortho-positions to the carbon atom bonded to theoxygen atom, if x=2, R¹ is C₂ -C₁₈ alkylene which is interrupted by--NR⁵ --, --O-- or --S--, or is a ##STR35## radical, and, if x=3, R¹ isC₄ -C₁₂ alkanetriyl or a ##STR36## group in which m is 1-4.
 2. Acomposition according to claim 1 where in the compound of formula I, ifx=1, R¹ is C₁ -C₃₀ alkyl, C₁ -C₁₈ alkyl substituted by halogen, --COOR²,--CN, --NR³ R⁴ or by --CONR³ R⁴, C₂ -C₁₈ alkyl which is interrupted by--NR⁵ --, --O-- or --S--, C₃ -C₁₈ alkenyl, C₃ -C₁₂ cycloalkyl, phenyl-C₁-C₄ alkyl, unsubstituted phenyl, or R¹ is naphthyl, a radical of theformula ##STR37## if x=2, R¹ is C₂ -C₁₈ alkylene which is interrupted by--NR⁵ --, --O-- or --S--, or is a ##STR38## radical, and, if x=3, R¹ isC₄ -C₁₂ alkanetriyl or a ##STR39## group in which m is 1-4.
 3. Acomposition according to claim 2 where in the compound of formula I, ifx=1, R¹ is C₁ -C₂₄ alkyl, C₁ -C₁₂ alkyl substituted by halogen, --COOR²,--CN, --NR³ R⁴ or by --CONR³ R⁴, C₂ -C₁₈ alkyl which is interrupted by--NR⁵ --, --O-- or --S--, C₃ -C₁₈ alkenyl, C₅ -C₁₂ cycloalkyl, phenyl-C₁-C₄ alkyl, unsubstituted phenyl, or R¹ is naphthyl, a radical of theformula ##STR40## if x=2, R¹ is C₂ -C₁₂ alkylene which is interrupted by--NR⁵ --, --O-- or --S--, or is a ##STR41## radical, and R¹⁰ and R¹¹,independently of one another, are hydrogen or C₁ -C₄ alkyl, and,if x=3,R¹ is C₄ -C₁₂ alkanetriyl or a ##STR42## group in which m is 1-4.
 4. Acomposition according to claim 3 where in the compound of formula I, ifx=1, R¹ is C₁ -C₂₀ alkyl, C₁ -C₈ alkyl which is substituted by halogen,--COOR², --CN or --NR³ R⁴, C₂ -C₈ alkyl which is interrupted by --O-- or--S--, C₃ -C₈ alkenyl, C₅ -C₈ cycloalkyl, unsubstituted phenyl, or R¹ isnaphthyl, a radical of the formula ##STR43## R⁶ is hydrogen or methyl,and R⁸ and R⁹ are hydrogen, if x=2, R¹ is C₂ -C₈ alkylene which isinterrupted by --NR⁵ -- or --O--, andif x=3, R¹ is a ##STR44## radical.5. A composition according to claim 3 where in the compound of formulaI, if x=1, R¹ is C₁ -C₁₈ alkyl which is unsubstituted or substituted byhalogen, --COOR², --CN or --NR³ R⁴, C₂ -C₁₈ alkyl which is interruptedby --NR⁵ --, --O-- or --S--, C₃ -C₆ alkenyl, C₅ -C₈ cycloalkyl,phenyl-C₁ -C₄ alkyl, a radical of the formula ##STR45## and, if x=2, R¹is C₂ -C₁₂ alkylene which is interrupted by --NR⁵ --, --O-- or --S--, oris a ##STR46## radical, and, if x=3, R¹ is C₄ -C₁₂ alkanetriyl or a##STR47## group.
 6. A composition according to claim 5 where in thecompound of formula I, x=1, R¹ is C₁ -C₁₂ alkyl which is unsubstitutedor substituted by halogen, --COOR², --CN or --NR³ R⁴, or R¹ is C₂ -C₁₂alkyl which is interrupted by --NR⁵ --, --O-- or --S--, or R¹ is C₅ -C₇cycloalkyl or phenyl-C₁ -C₄ alkyl.
 7. A composition according to claim 1where in the compound of formula I, R¹ is C₁ -C₁₈ alkyl, C₅ -C₇cycloalkyl or phenyl-C₁ -C₄ alkyl.
 8. A composition according to claim 7wherein R¹ is C₁ -C₄ alkyl.
 9. A composition according to claim 1, inwhich component (a) is a natural, semisynthetic or synthetic polymer.10. A composition according to claim 9, in which component (a) is athermoplastic polymer.
 11. A composition according to claim 9, in whichcomponent (a) is a polyolefin.
 12. A composition according to claim 9,in which component (a) is a polyvinyl chloride, a polyethylene or apolypropylene.
 13. A method of stabilizing organic materials againstoxidative, thermal and/or actinic degradation, which comprises adding orapplying, as stabiliser, at least one compound of the formula Iaccording to claim 1 to this material.